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Keywords = push–pull thienylthiazole

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17 pages, 4236 KB  
Article
Synthesis and Strong Solvatochromism of Push-Pull Thienylthiazole Boron Complexes
by Martijn J. Wildervanck, Reinhard Hecht and Agnieszka Nowak-Król
Molecules 2022, 27(17), 5510; https://doi.org/10.3390/molecules27175510 - 27 Aug 2022
Cited by 9 | Viewed by 3337
Abstract
The solvatochromic behavior of two donor-π bridge-acceptor (D-π-A) compounds based on the 2-(3-boryl-2-thienyl)thiazole π-linker and indandione acceptor moiety are investigated. DFT/TD-DFT calculations were performed in combination with steady-state absorption and emission measurements, along with electrochemical studies, to elucidate the effect of two different [...] Read more.
The solvatochromic behavior of two donor-π bridge-acceptor (D-π-A) compounds based on the 2-(3-boryl-2-thienyl)thiazole π-linker and indandione acceptor moiety are investigated. DFT/TD-DFT calculations were performed in combination with steady-state absorption and emission measurements, along with electrochemical studies, to elucidate the effect of two different strongly electron-donating hydrazonyl units on the solvatochromic and fluorescence behavior of these compounds. The Lippert–Mataga equation was used to estimate the change in dipole moments (Δµ) between ground and excited states based on the measured spectroscopic properties in solvents of varying polarity with the data being supported by theoretical studies. The two asymmetrical D-π-A molecules feature strong solvatochromic shifts in fluorescence of up to ~4300 cm1 and a concomitant change of the emission color from yellow to red. These changes were accompanied by an increase in Stokes shift to reach values as large as ~5700–5800 cm1. Quantum yields of ca. 0.75 could be observed for the N,N-dimethylhydrazonyl derivative in nonpolar solvents, which gradually decreased along with increasing solvent polarity, as opposed to the consistently reduced values obtained for the N,N-diphenylhydrazonyl derivative of up to ca. 0.20 in nonpolar solvents. These two push–pull molecules are contrasted with a structurally similar acceptor-π bridge-acceptor (A-π-A) compound. Full article
(This article belongs to the Special Issue New Boron Chemistry: Current Advances and Future Prospects)
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